EP0446869B2 - Verfahren zur Herstellung von 1,1,1-Trifluorchlorethan und 1,1,1,2-Tetrafluorethan - Google Patents

Verfahren zur Herstellung von 1,1,1-Trifluorchlorethan und 1,1,1,2-Tetrafluorethan Download PDF

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Publication number
EP0446869B2
EP0446869B2 EP19910103753 EP91103753A EP0446869B2 EP 0446869 B2 EP0446869 B2 EP 0446869B2 EP 19910103753 EP19910103753 EP 19910103753 EP 91103753 A EP91103753 A EP 91103753A EP 0446869 B2 EP0446869 B2 EP 0446869B2
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EP
European Patent Office
Prior art keywords
reactor
hydrogen fluoride
tetrafluoroethane
process according
chloroethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP19910103753
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English (en)
French (fr)
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EP0446869B1 (de
EP0446869A1 (de
Inventor
Satoshi C/O Yodogawaseisakusho Of Koyama
Yukio C/O Yodogawaseisakusho Of Homoto
Naoki C/O Yodogawaseisakusho Of Esaka
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority claimed from JP2285596A external-priority patent/JPH07100671B2/ja
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Priority to EP94116343A priority Critical patent/EP0648726A2/de
Priority to EP94105545A priority patent/EP0610963A3/de
Publication of EP0446869A1 publication Critical patent/EP0446869A1/de
Publication of EP0446869B1 publication Critical patent/EP0446869B1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms

Definitions

  • R-133a and hydrogen fluoride are supplied in the second reactor.
  • the reaction product from the second reactor is a gaseous mixture (the "first gaseous mixture") of desired R-134a, unreacted R-133a and hydrogen fluoride, and by-products including R-1122.
  • the first gaseous mixture is directly supplied to the first reactor together with the raw material, namely trichloroethylene.
  • a fluorination catalyst was produced. Prior to use, the catalyst was fluorinated with hydrogen fluoride. Forty grams of the catalyst was filled in a Hastelloy C tube of 20 mm in inner diameter and 700 mm in length and heated to 320°C in a nitrogen stream. Then, the supply of nitrogen was stopped and trichloroethylene and hydrogen fluoride were supplied at flow rates of 85 ml/min. and 420 ml/min., respectively. As soon as trichloroethylene and hydrogen fluoride were supplied, an exothermic reaction started and the maximum temperature reached 345°C.
  • the conversion of trichloroethylene was 98 %, and the selectivity was 96 %.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (12)

  1. Verfahren zur Herstellung von 1,1,1,2-Tetrafluorethan, das die folgenden Schritte umfasst:
    (i) Fluorierung von Trichlorethylen in der Gasphase mit Fluorwasserstoff in Anwesenheit eines Fluorierungskatalysators in einem ersten Reaktor unter Bildung von 1,1,1-Trifluor-2-chlorethan; und
    (ii) Fluorierung des 1,1,1-Trifluor-2-chlorethans in der Gasphase mit Fluorwasserstoff Anwesenheit eines Fluorierungskatalysators in einem zweiten Reaktor unter Bildung einer ersten gasförmigen Mischung, die 1,1,1,2-Tetrafluorethan, nicht-reagiertes 1,1,1-Trifluor-2-chlorethan und 1,1-Difluorchlorethylen als Nebenprodukt umfasst, dadurch gekennzeichnet, dass
    (a) mindestens ein Teil der ersten gasförmigen Mischung in den ersten Reaktor eingebracht wird, wo es als Verdünnungsmittel in dem Fluorierungsschritt (i) fungiert, und worin das 1,1-Difluorchlorethylen mit Fluorwasserstoff zu 1,1,1-Trifluor-2-chlorethan fluoriert wird, und
    (b) das 1,1,1,2-Tetrafluorethan aus der Gasmischung, die aus dem Fluorierungsschritt (i) resultiert, abgetrennt wird.
  2. Verfahren gemäss Anspruch 1, worin der Fluorierungsschritt (i) bei einer Temperatur von 180-300°C durchgeführt wird.
  3. Verfahren gemäss Anspruch 1 oder 2, worin der Fluorierungsschritt (ii) bei einer Temperatur von 300-400°C durchgeführt wird.
  4. Verfahren gemäss Anspruch 3, das den weiteren Schritt der Zuführung der aus dem Fluorierungsschritt (i) resultierenden Gasmischung in einen dritten Reaktor umfasst, worin die Menge an 1,1-Difluorchlorethylen vor dem Schritt der Abtrennung von 1,1,1,2-Tetrafluorethan aus der Gasmischung verringert wird.
  5. Verfahren gemäss Anspruch 4, worin der dritte Reaktor bei einer Temperatur von 180-300°C betrieben wird.
  6. Verfahren gemäss mindestens einem der vorangegangenen Ansprüche, worin das Volumen der ersten gasförmigen Mischung, die in den ersten Reaktor eingebracht wird, das 1- bis 40-fache des Volumens an Trichlorethylen beträgt.
  7. Verfahren gemäss mindestens einem der vorangegangenen Ansprüche, worin die gesamte Gasmischung, die aus dem Fluorierungsschritt (ii) resultiert, in den ersten Reaktor eingebracht wird.
  8. Verfahren zur Herstellung von 1,1,1,2-Tetrafluorethan, das folgende Schritt umfasst:
    (1) Reaktion von Trichlorethylen mit Fluorwasserstoff in der Gasphase in Gegenwart eines Fluorierungskatalysators unter Erhalt von 1,1,1-Trifluorchlorethan in einem ersten Reaktor;
    (2) Reaktion von 1,1,1-Trifluor-2-chlorethan aus dem ersten Reaktor mit Fluorwasserstoff in der Gasphase in Gegenwart eines Fluorierungskatalysators unter Erhalt von 1,1,1,2-Tetrafluorethan und dem Nebenprodukt 1,1-Difluorchlorethylen in einem zweiten Reaktor;
    (3) Recyclierung der gesamten Reaktionsmischung, einschliesslich 1,1,1,2-Tetrafluorethan und nicht-reagiertem 1,1,1-Trifluor-2-chlorethan aus dem zweiten Reaktor in den ersten Reaktor;
    (4) Reaktion von 1,1-Difluorchlorethylen, das in dem zweiten Reaktor erzeugt wurde, mit Fluorwasserstoff unter Reduzierung der Menge an 1,1-Difluorchlorethylen in dem ersten Reaktor; und
    (5) Abtrennung von 1,1,1,2-Tetrafluorethan aus der in dem ersten Reaktor erhaltenen Gasmischung, bevor diese Mischung in den zweiten Reaktor eingeführt wird.
  9. Verfahren gemäss Anspruch 8, worin die Reaktion (1) bei einer Temperatur von 180-300°C und die Reaktion (2) bei einer Temperatur von 300-400°C durchgeführt wird.
  10. Verfahren gemäss Anspruch 8, worin das Molverhältnis von Fluorwasserstoff zu 1,1,1-Trifluor-2-chlorethan in dem zweiten Reaktor im Bereich von 2:1 bis 10:1 liegt.
  11. Verfahren gemäss Anspruch 8, worin der Fluorwasserstoff, der für beide Reaktionen in den Schritten (1) und (2) benötigt wird, in den zweiten Reaktor eingebracht wird.
  12. Verfahren gemäss Anspruch 8, worin die in den Schritten (1) und (2) verwendeten Fluorierungskatalysatoren thermisch behandeltes Chromhydroxid umfassen.
EP19910103753 1990-03-13 1991-03-12 Verfahren zur Herstellung von 1,1,1-Trifluorchlorethan und 1,1,1,2-Tetrafluorethan Expired - Lifetime EP0446869B2 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP94116343A EP0648726A2 (de) 1990-03-13 1991-03-12 Verfahren zur Herstellung von 1,1,1,2,-Tetrafluorethan
EP94105545A EP0610963A3 (de) 1990-03-13 1991-03-12 Verfahren zur Herstellung von 1,1,1,2-Tetrafluoroethan.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP6181190 1990-03-13
JP6181190 1990-03-13
JP61811/90 1990-03-13
JP2285596A JPH07100671B2 (ja) 1990-03-13 1990-10-22 １，１，１，２―テトラフルオロエタンの製造方法
JP285596/90 1990-10-22
JP28559690 1990-10-22

Related Child Applications (3)

Application Number Title Priority Date Filing Date
EP94116343.8 Division-Into 1991-03-12
EP94105545.1 Division-Into 1991-03-12
EP94105545A Division EP0610963A3 (de) 1990-03-13 1991-03-12 Verfahren zur Herstellung von 1,1,1,2-Tetrafluoroethan.

Publications (3)

Publication Number Publication Date
EP0446869A1 EP0446869A1 (de) 1991-09-18
EP0446869B1 EP0446869B1 (de) 1996-03-20
EP0446869B2 true EP0446869B2 (de) 2003-02-12

Family

ID=26402891

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910103753 Expired - Lifetime EP0446869B2 (de) 1990-03-13 1991-03-12 Verfahren zur Herstellung von 1,1,1-Trifluorchlorethan und 1,1,1,2-Tetrafluorethan

Country Status (10)

Country Link
EP (1) EP0446869B2 (de)
KR (1) KR960004869B1 (de)
CN (1) CN1033321C (de)
AU (1) AU645063B2 (de)
BR (1) BR9100978A (de)
CA (1) CA2038026C (de)
CZ (1) CZ280000B6 (de)
DE (1) DE69118002T3 (de)
ES (1) ES2087171T5 (de)
GR (1) GR3019391T3 (de)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5185482A (en) * 1989-02-03 1993-02-09 E. I. Du Pont De Nemours And Company Manufacture of 1,1,1,2-tetrafluoroethane
IT1230779B (it) * 1989-07-12 1991-10-29 Ausimont Srl Procedimento per preparare 1,1,1,2 tetrafluoroetano.
GB9007029D0 (en) * 1990-03-29 1990-05-30 Ici Plc Chemical process
US5444171A (en) * 1992-10-14 1995-08-22 Showa Denko Kabushiki Kaisha Method for purification of 1,1,1,2-tetrafluoroethane
JP2661441B2 (ja) * 1991-11-27 1997-10-08 ダイキン工業株式会社 １，１，１−トリフルオロ−２−クロロエタンおよび／または１，１，１，２−テトラフルオロエタンの製法
FR2694556B1 (fr) 1992-08-05 1994-09-23 Atochem Elf Sa Procédé de purification du 1,1,1,2-tétrafluoroéthane.
TW227550B (de) * 1992-08-05 1994-08-01 Showa Denko Kk
TW228512B (de) * 1992-08-10 1994-08-21 Showa Denko Kk
IT1255781B (it) * 1992-08-14 1995-11-15 Ausimont Spa Procedimento per preparare 1,1,1-trifluoro-2-cloroetano
US5409625A (en) * 1993-05-24 1995-04-25 E. I. Du Pont De Nemours And Company Azeotropic mixture of linear hydrofluorocarbon and HF
FR2736050B1 (fr) 1995-06-29 1997-08-01 Atochem Elf Sa Procede de fabrication du difluoromethane
US5654494A (en) * 1995-08-18 1997-08-05 Alliedsignal Inc. Process for the manufacture of 1,1,1,2-tetrafluoroethane
CN101402547B (zh) * 2008-11-13 2011-09-28 山东华安新材料有限公司 一种一氯三氟乙烷的制法
CN104892353A (zh) * 2015-06-02 2015-09-09 江苏三美化工有限公司 一种提高气相氟化制备1,1,1,2-四氟乙烷转化率的方法
CN108623431A (zh) * 2018-06-28 2018-10-09 江苏三美化工有限公司 一种通过净化反应提纯1,1,1,2-四氟乙烷的方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4792643A (en) * 1987-06-16 1988-12-20 Kaiser Aluminum & Chemical Corporation Catalyst and process for 1,1,1,2-tetrafluoroethane by vapor phase reaction
CA1310335C (en) * 1988-02-12 1992-11-17 Leo E. Manzer Gas-phase fluorination process
DE69023759T3 (de) * 1989-02-03 2004-05-13 E.I. Du Pont De Nemours And Co., Wilmington Verfahren zur herstellung von 1,1,1,2-tetrafluoroäthan.
IT1230779B (it) * 1989-07-12 1991-10-29 Ausimont Srl Procedimento per preparare 1,1,1,2 tetrafluoroetano.

Also Published As

Publication number Publication date
DE69118002T3 (de) 2003-10-09
CS9100656A2 (en) 1991-11-12
ES2087171T3 (es) 1996-07-16
ES2087171T5 (es) 2003-10-16
KR960004869B1 (en) 1996-04-16
CN1055534A (zh) 1991-10-23
CN1033321C (zh) 1996-11-20
EP0446869B1 (de) 1996-03-20
DE69118002D1 (de) 1996-04-25
GR3019391T3 (en) 1996-06-30
CZ280000B6 (cs) 1995-09-13
AU645063B2 (en) 1994-01-06
BR9100978A (pt) 1991-11-05
CA2038026A1 (en) 1991-09-14
AU7281591A (en) 1991-09-19
EP0446869A1 (de) 1991-09-18
DE69118002T2 (de) 1996-09-19
CA2038026C (en) 2002-05-07

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